High-Temperature Hydrogen Sensors Based on Gallium Oxide Heterojunction Diodes

Abstract

Long-term, high temperature operation of Ga2O3 devices is a crucial hurdle that must be overcome before widespread adoption of the technology can be achieved, but is largely absent from the overall body of work. Demonstrations up to this point show devices are either limited by material or dopant instability that leads to performance degradation with time. Herein, Ga2O3-based hydrogen sensors employing Pt Schottky and Cr2O3/Ga2O3 p-n diodes (Mg- and N-doped) were fabricated and evaluated for long-term stability at 600C for 800-1,800 hours, with cyclic exposure to N2 and low-concentration H2 (500-1,500 ppm). Transient current density (measured at -0.1 V) and periodic J-V characterization were used to track performance. Despite gradual declines in sensor signal and sensitivity, devices distinguished hydrogen concentrations throughout weeks of operation. Degradation was architecture-dependent: Cr2O3:Mg degraded gradually, consistent with known Mg migration; the Pt Schottky diode showed dramatic changes after 1,000 hours; and Cr2O3:N showed the lowest but most stable performance before failing at 800 hours. Thermionic emission and Lambert W-based modeling confirmed hydrogen exposure reduces interfacial barrier height via a proton-induced dipole mechanism common to both diode types. TEM of aged Pt Schottky diodes revealed Pt grain growth and microvoid formation as key degradation mechanisms. TOF-SIMS confirmed nitrogen dopants remain confined to the Cr2O3:N layer, supporting N-doping as a stable, lower-performance alternative to Mg-doping